The workability of fresh Portland cement (PC) concrete critically depends on the reaction of the cubic tricalcium aluminate (C(3)A) phase in Ca- and S-rich pH >12 aqueous solution, yet its rate-controlling mechanism is poorly understood. In this article, the role of adsorption phenomena in C(3)A dissolution in aqueous Ca-, S-, and polynaphthalene sulfonate (PNS)-containing solutions is analyzed. The zeta potential and pH results are consistent with the isoelectric point of C(3)A occurring at pH-42 and do not show an inversion of its electric double layer potential as a function of S or Ca concentration, and PNS adsorbs onto C(3)A, reducing its zeta potential to negative values at pH >12. The S and Ca Kedge X-ray absorption spectroscopy (XAS) data obtained do not indicate the structural incorporation or specific adsorption of 5042 on the partially dissolved C(3)A solids analyzed. Together with supporting X-ray ptychography and scanning electron microscopy results, a model for C(3)A dissolution inhibition in hydrated PC systems is proposed whereby the formation of an Al-rich leached layer and the complexation of Ca-S ion pairs onto this leached layer provide the key inhibiting effect(s). This model reconciles the results obtained here with the existing literature, including the inhibiting action of macromolecules such as PNS and polyphosphonic acids upon C(3)A dissolution. Therefore, this article advances the understanding of the rate-controlling mechanism in hydrated C(3)A and thus PC systems, which is important to better controlling the workability of fresh PC concrete.